Process for breaking petroleum emulsions employing certain polyepoxide treated derivatives obtained by reaction of monoepoxides with resins



a r 2,771,430 Patented Nov. 20; 1956 i ater SIONS EMPLOYING CERTAIN POLYEPOXIDE the divalent TREATED DERIVATIVES OBTAINED BY REAC- TION OF MGNOEPOXIDES WITH RESINS 5 Melvin De Groote, University City, and Kwan-Ting Shen, Brentwood, M0., assignors to Petrolite Corporation,

radical, the divalent sulfone radical, and the divalent Wilmington, Del., a corporation f D l monosulfide radical -S, the divalent radical No Drawing. Application April 22, 1953, CH2SCH2 Serial No. 350,531 and the divalent disulfide radical SfiS-; and R10 is. the divalent radical obtained by the elimination of a hy-, 20 Claims 252 338) droxyl hydrogen atom and a nuclear hydrogen atom from The present invention is a continuation-impart of our the phenol co-pending application, Serial No. 305,079, filed August 18, 1952, now abandoned. 011

Our invention provides an economical and rapid process for resolving petroleum emulsions of the water-in-oil type that are commonly referred to as cut oil, roily oil, emulsified oil, etc., and which comprise fine droplets of naturally-occurring Waters or brines dispersed in in which R, R", and R represent hydrogen and hydro a more or less permanent state throughout the oil which carbon substituents of the aromatic nucleus, said subconstitutes the continuous phase of the invention. stituent member having not over 18 carbon atoms.

It also provides an economical and rapid process for A further limited aspect of the invention is represented separating emulsions which have been prepared under by the use of such products wherein the oxyalkylated resin controlled conditions from mineral oil, such as crude condensate is reacted with a member of the class of (a) oil and relatively soft waters or weak brines. Controlled Compounds of the following formula: emulsification and subsequent demulsification under the conditions just mentioned are of significant value in removing impurities, particularly inorganic salts, from pipe- C R" line oil.

Attention is directed to two co-pending De Groote ap- 2 plications, Serial No. 310,551, filed September 19, 1952, wherein R is essentially an aliphatic hydrocarbon bridge,

now Patent No. 2,695,887, and Serial No. 333,386, filed each n independently has one of the values 0 to 1, and January 26, 1953. These two applications describe hy- R1 is an alkyl radical containing from 1 to 4 carbon atoms,.

drophile products obtained by the oxyalkylation of the or even 12 carbon atoms, and (b) cogenerically associcondensation product of certain phenolaldehyde resins ated compounds formed in the preparation of (a) prewith respect to nonhydroxylated secondary monoamines ceding, including monoepoxides. and formaldehyde. Reference herein to being thermoplastic or non-thermo- The present invention is concerned with the breaking setting characterizes products as being liquids at ordinaryof water-in-oil emulsions by the use of products obtained temperature or readily convertible to liquids by merely by reacting said oxyalkylated derivatives of the kind just heating below the point of pyrolysis and thus diiferentidescribed with a phenolic polyepoxide of the kind previates them from infusible resins. Reference to being ously described in our aforementioned co-pending apsoluble in an organic solvent means any of the usualplication, Serial No. 305,079. organic solvents, such as alcohols, ketones, esters, ethers, Thus the present invention is concerned with the use of mixed solvents, etc. Reference to solubility is merely to products of reaction obtained by a 3-step manufacturing differentiate from a reactant which is not soluble and process involving (1) condensing certain phenol aldehyde might be not only insoluble but also infusible. Furtherresins, hereinafter described in detail, with certain basic more, solubility is afactor insofar that it is sometimes nonhydroxylated secondary monoamines, hereinafter dedesirable to dilute the compound containing the epoxy scribed in detail, and formaldehyde; (2) oxyalkylation of rings before reacting with the monoepoxide-derived prod! the condensation product with certain monoepoxides,herenot. In such instances, of course, the solvent selected inafter described in detail; and (3) oxyalkylation of the would have to be one which is not susceptible to oxyalkylapreviously oxyalkylated resin condensate with certain tion, as for example, kerosene, benzene, toluene, dioxane, phenolic polyepoxides, hereinafter described in detail, various ketones, chlorinate S vents, dibutyl ether, dihexyl and cogenerically associated compounds formed in their ether, ethyleneglycol diethylether, d'iethyleneglycol di-- preparation. ethylether, and dirnethoxytetraethyleneglycol.

A more limited aspect of the present invention is con- The expression epoxy is not usually limited to the cerned with the use of such products of reaction wherein 1,2-ep0xy ring. The 1,2-epoxy ring is sometimes referred the oxyalkylated resin condensate is reacted with a to as the oxirane ring to distinguish it from other epoxy member of the class of compounds of the following rings. Hereinafter the word epoxy unless indicated formula: otherwise, will e s v t mean the xir ne r ng, ie, he

l oo-o oR1[R],.-R1o-oo 0- OR1[R],,R10C-G--O H: H H2 H: (I) H: H: H H:

in which R represents a divalent radical selected from the 1,2-cpoxy ring. Furthermore, where a compound has class consisting of ketone residues formed by the eliminatwo or more oxirane rings they will be referred to as tion of the ketonic oxygen atom and aldehyde residues polyepoxides. They usually represent, of course, 1,2- obtained by the elimination of the aldehydic oxygen epoxy rings or oxirane rings in the alpha-omega position. atom; the divalent radical This is a departure, of course, from the standpoint of simplest diepoxide which contains at least 4 carbon atoms and is formally described as 1,2-epoxy-3,4-epoxybutane( 1,2,3,4, diepoxybutane).

It well may be that even though the previously suggested formula represents the principal component, or components, of the resultant or reaction product described in the previous text, it may be important to note that somewhat similar compounds, generally of much higher molecular weight, have been described as complex resinous epoxides which are polyether derivatives of poly hydric phenols containing an average of more than one epoxide group per molecule and free from functional groups other than epoxide and hydroxyl groups. See U. S. Patent No. 2,494,295, dated January 10, 1950, to Greenlee. The compounds here included are limited to the monomers or the low molal members of such series and generally contain two epoxide rings per molecule and may be entirely free from a hydroxyl group. This is important because the instant invention is directed towards products which are not insoluble resins and have certain solubility characteristics not inherent in the usual thermosetting resins.

Having obtained a reactant having generally 2 epoxy rings as depicted in the last formula preceding, or low molal polymers thereof, it becomes obvious the reaction can take place with any oxyalkylated phenol-aldedhyde resin by virtue of the fact that there are always present either phenolic hydroxyl radicals or alkanol radicals resulting from the oxyalkylation of the phenolic hydroxyl radicals; there may be present reactive hydrogen atoms attached to a nitrogen atom or an oxygen atom, depending on Whether initially there was present a hydroxylated group attached to an amino hydrogen group or a secondary amino group. In any event there is always a multiplicity of reactive hydrogen atoms present in the oxyalkylated amine-modified phenol-aldehyde resin.

To illustrate the products which represent the subject matter of the present invention reference will be made to a reaction involving a mole of the oxyalkylating agent, i. c., the compound having two oxirane rings and an oxyalkylated amine condensate. Proceeding with the example previously described it is obviousthe reaction ratio of two moles of the oxyalkylated amine condensate to one mole of the oxyalkylating agent gives a product which may be indicated as follows:

'temperature and show at least some tendency towards being self-dispersing. The solvent which is generally tried is xylene. If xylene alone does not serve then a mixture of xylene and methanol, for instance, 80 parts of xylene and 20 parts of methanol, or 70 parts of xylene and 30 parts of methanol, can be used. Sometimes it is desirable to add a small amount of acetone to the xylenemethanol mixture, for instance, 5% to 10% of acetone. As oxyalkylation proceeds the significance of the basicity of any nitrogen group is obviously diminished.

For purpose of resolution of petroleum emulsions of the water-in-oil type, we particularly prefer to use those products which as such or in the form of the free base or hydrate, i. e., combination with water or particularly in the form of a low molal organic acid salt such as the gluconates or the acetate or hydroxy acetate, have sufiiciently hydrophile character to at least meet the test set forth in U. S. Patent No. 2,499,368, dated March 7, 1950, to De Groote et a1. In said patent such test for emulsification using a water-insoluble solvent, generally xylene, is described as an index of surface activity.

.In the present instance the various condensation products as such or in the form of the free base or in the form of the acetate, may not necessarily be xylene-soluble although they are in many instances. If such compounds are not xylene-soluble the obvious chemical equivalent or equivalent chemical test can be made by simply using some suitable solvent, preferably a water-soluble solvent such as ethylene glycol diethylether, or a low molal alcohol, or a mixture to dissolve the appropriate product being examined and then mix with the equal weight of xylene, followed by addition of Water. Such test is obviously the same for the reason that there Will be two phases on vigorous shaking and surface activity makes its presence manifest. It is understood the reference in the hereto appended claims as to the use of xylene in the emulsification test includes such obvious variant.

For purpose of convenience, what is said hereinafter will be divided into nine parts with Part 3, in turn,

being divided into three subdivisions:

Part 1 is concerned with our preference in regard to the polyepoxide and particularly the diepoxide reactant;

Part 2 is concerned with certain theoretical aspects of diepoxide preparation;

(oxyalkylated condensate) in which the various characters have their previous significance and the characterization oxyalkylated condensate is simply an abbrevation for the oxyalkylated condensate which is described in greater detail subsequently.

Such final product in turn also must be soluble but solubility is not limited to an organic solvent but may include water, or for that matter, a solution of water containing an acid such as hydrochloric acid, acetic acid, hydroxyacetic acid, etc. Inother words, the nitrogen groups present, whether two or more, may or may not be significantly basic and it is immaterial whether aqueous solubility represents an anhydro base or the free base (combination with water) or a salt form such as the acetate, chloride, etc. The purpose in this instance is to differentiate from insoluble resinous materials, particularly those resulting from gelation or criss-linking. Not

only does this property serve to differentiate from in-' to 20 times their weight of 5% gluconic acid at ordinary.

condensate) Part 3, Subdivision A, is concerned with the preparation of monomeric diepoxides, including Table I;

Part 3, Subdivision B, is concerned with the preparation of low molal polymeric epoxides or mixtures containing low molal polymeric epoxides as well as the monomer and includes Table II;

Part 3, Subdivision C, is concerned with miscellaneous phenolic reactants suitable for diepoxide preparation;

Part 4 is concerned with the phenol-aldehyde resin which is subjected to modification by condensation reaction to yield an amine-modified resin; 7

Part 5 is concerned with appropriate basic secondary amines free from a hydroxyl radical which may be employed in the preparation of the herein-described aminemodified resins;

Part 6 is concerned with reactions involving the resin, the amine, and formaldehyde to produce specific products or compounds which are then subjected to oxyalkylation with monoepoxides; 1

Part 7 is concerned with the oxyalkylation of the products described in Part 6, preceding;

preceding types of materials and examples obtained by such reactions. Generally speaking, this involves nothing more than a reaction between two moles of a previously-prepared oxyalkylated amine-modified phenol-aldehyde resin condensate as described and one mole of a polyepoxide so as to yield a new and larger resin molecular comparable product;

Part 9 is concerned with the resolution of petroleum emulsions of the water-in-oil type by means of the previously described chemical compounds or reaction products.

PART 1 As will be pointed out subsequently, the preparation of polyepoxides may include the formation of a small amount of material having more than two epoxide groups per molecule. If such compounds are formed they are perfectly suitable except to the extent they may tend to produce ultimate reaction products which are not 'solvent-soluble liquids or low-melting solids. Indeed, they tend to form thermosetting resins or insoluble materials. Thus, the specific objective by and large is to produce diepoxides as free as possible from any monm epoxides and as free as possible from polyepoxides in which there are more than two epoxide groups per molecule. Thus, for practical purposes what is said hereinafter is largely limited to polyepoxides in the form of diepoxides.

As has been pointed out previously one of the reactants employed is a diepoxide reactant. It is generally obtained from phenol (hydroxybenzene) or substituted phenol. The ordinary or conventional manufacture of the epoxides usually results in the formation of a cogeneric mixture as explained subsequently. Preparation of the monomer or separation of the monomer from the remaining mass of the co-generic mixture is usually expensive. If monomers were available commercially at a low cost, or if they could be prepared without added expense for separation, our preference would be to use the monomer. Certain monomers have been prepared and described in the literature and will be referred to subsequently. However, from a practical standpoint one must weigh the advantage, if any, that the monomer has over other low molal polymers from a cost standpoint; thus, we have found that one might as well attempt to prepare a monomer and fully recognize that there maybe present, and; probably invariably arepresent, other 'low molal polymers in comparatively small amounts. Thus, the materials which are most apt to be used for practical reasons are either monomers with some small amounts of polymers present or mixtures which have a substantial amount of polymers present. Indeed, the mixture can be prepared free from monomers and still be satisfactory. Briefly, then, our preference is to use the monomer or the monomer with the minimum amount of higher polymers.

It has been pointed out previously that the phenolic nuclei in the epoxide reactant may be directly united, or united through a variety of divalent radicals. Actually, it is our preference to use those which are commercially available and for most practical purposes it means instances where the phenolic nuclei are either united directly without any intervening linking radical, or else united by a ketone residue or formaldehyde residue. The commercial bis-phenols available now in the open market illustrate one class. The diphenyl derivatives illustrate a second class, and the materials obtained by reacting substituted monofunctional phenols with an aldehyde illustrate the third class. All the various known classes may be used but our preference rests with these classes due to their availability and ease of preparation, and also due to the fact that the cost is lower than in other examples.

Although the diepoxide reactants can be produced in more than one way, as pointed out elsewhere, our pref- 6 erence is to produce them by means of the epichlorohydrin reaction referred to in detail subsequently.

One epoxide which can be purchased in the open market and contains only a modest amount of polymers corresponds to the derivative of bis-phenol A. It can be used as such, or the monomer can be separated by an added step which involves additional expense. This compound of the following structure is preferred as the epoxide reactant and will be used for illustration re.- peatedly with the full understanding that any of the other epoxides described are equally satisfactory, or that the higher polymers are satisfactory, or that mixtures. of, the monomer and higher polymers are satisfactoryf The formula for this compound is Reference has just been made to bis-phenol A and a suitable epoxide derived therefrom. Bis-phenol A is dihydroxy-diphenyldimethyl methane, with the 4,4 isomers predominating and with lesser quantities of the 2,2 and 4,2 isomers being present. It is immaterial which one of these isomers is used and the commercially available mixture is entirely satisfactory.

Attention is again directed to the fact that in the instant part, to wit, Part 1, and insucceedingparts, the text is concerned almost entirely with epoxides in which there is no bridging radical or the bridging radical is derived from an'aldehyde or a ketone. It would be immaterial if the divalent linking radical would be derived from the other groups illustrated for the reason that nothing more than mere substitution of one; compound for. the other would be required. Thus, what issaid hereinafter, although directed to one class or a few classes, applies with equal force and effect to theother classes of epoxide reactants.

if sulfur-containing compounds. are. prepared they should be freed from impurities with considerable care for the reason that any time that'a low-molal sulfur-containing compound can react with epichlorohydrin there may be formed a by-productin which the chlorine happenedto be particularly. reactive and may represent a product, or a mixtureof products, which would be unusually toxic, even though in comparatively small concentration.

PART 2 The polyepoxi des and particularly the diepoxides can be derived by morethan one method as, for example, the use of epichlorohydrin or glycerol dichlorohydrin. If a product such as bis-phenol A is employed the ultimate compound in monomeric form employed as a reactant in the present invention has the following'structure:

Treatment withepichlorohydrin, for example, does not-- yield this product initially but there is an intermediate produced which can be indicated by the following structure:

Treatment with. alkali, of ,course forms the poxy ring. A

of reasons is that one obtains a product in which there is only one epoxide ring and there may, as a matter of fact, be more than one hydroxyl radical as illustrated by the following compounds:

(2) Even if one starts with the reactants in the preferred r CH ratio, to wit, two parts of epichlorohydrin to one part of bis-phenol A, they do not necessarily so react and as a result one may obtain products in which more than two epichlorohydrin residues become attached to a single bisphenol A nucleus by virtue of the reactive hydroxyls present which enter into oxalkylation reactions rather than ring closure reactions.

(3) As is well known, ethylene oxide in the presence of alkali, and for that matter in the complete absence of water, forms cyclic polymers. Indeed, ethylene oxide can produce a solid polymer. This same reaction can, and at times apparently does, take place in connection with compounds having one, or in the present instance, two substituted oxirane rings, i. e., substituted, 1,2 epoxy rings. Thus, in many ways it is easier to produce a polymer, particularly a mixture of the monomer, dimer and trimer, than it is to produce the monomer alone.

(4) As has been pointed out previously, monoepoxides may be present and, indeed, are almost invariably and inevitably present when one attempts to produce polyepoxides, and particularly diepoxides. The reason is the one H: HH

which has been indicated previously, together with the fact that in the ordinary course of reaction a diepoxide, such as may react with a mole of bis-phenol A to give a monoepoxy structure. Indeed, in the subsequent text immediately following reference is made to the dimers, trimers and tetramers in which two epoxide groups are present. Needless to say, compounds can be formed which correspond in every respect except that one terminal epoxide group is absent and in its place is a group having one chlorine atom and one hydroxyl group, or else two hydroxyl groups, or an unreacted phenolic ring.

(5) Some reference has been made to the presence of 75 8 a chlorine atom and although all elfort is directed towards the elimination of any chlorine-containing molecule yet it is apparent that this is often an ideal approach rather than a practical possibility. Indeed, the same sort of reactants are sometimes employed to obtain products in which intentionally there is both an epoxide group and a chlorine atom present. See U. S. Patent No. 2,581,464, dated January 8, 1952, to Zech.

For purpose of brevity, without going any further, the next formula is in essence one which, perhaps in an idealized way, establishes the composition of resinous products available under the name of Epon Resins as now sold in the open market. See, also, chemical pamphlet entitled Epon Surface-Coating Resins, Shell Chemical Corporation, New York city. The word Epon is a registered trademark of the Shell Chemical Coporation.

pH; (|)H V I 13,

O on, (311:

OH I For the purpose of the instant invention, n may represent a number including zero, and at the most a low number such as 1, 2 or 3. This limitation does not exist in actual efforts to obtain resins as differentiated from the herein described soluble materials. It is quite probable 30 that in the resinous products as marketed for coating use the value of'n is usually substantially higher. Note again what has been said previously that any formula is, at best, an over-simplification, or at the most represents perhaps only the more important or principal constituent or con- 35 stituents. These materials may vary from simple nonresinous to complex resinous epoxides which are polyether derivatives of polyhydric phenols containing an average of more than one epoxide group per molecule and free from functional groups other than epoxide and hydroxyl In summary then in light of what has been said, compounds suitable for reaction with amines may be summarized by the following formula:

in which the various characters have their prior significance and in which R10 is the divalent radical obtained by the elimination of a hydroxyl hydrogen atom and a nuclear hydrogen atom from the phenol in which R, R", and Rf represent a member of the class consisting of hydrogen and hydrocarbon'substituents of the aromatic nucleus, said substituent member having not over 18 carbon atoms; n represents an integer selected from the class of zero and 1, and n represents a whole number not greater than 3.

PART 3 or diglycidyl ethersas they are sometimes termed, are in Subdivision A eluded for purpose of illustration. These particular com- The preparations of the diepoxy derivatives of the pounds are described in the two patents Just mentioned.

TABLE I Ex- Patent ample D iphenol Diglycldyl jether refernumber ence CHKCJLOH)? Dit poxypronoxyphenyl)methane 2,506,486

OHgOH (GENE); D1(ep0xypropoxyphenybmethylmethane 2, 506, 486

(GHmC (C H4OH)z Di(epoxypropoxyphsnyl) dimethylmethane" 2, 506, 486 O H O(OH3) (COH4OH)2 D1(epoxypropoxyphenyl)ethylmethylmethane. 2, 506, 486 (CzH5)2O(C H4OE "Di(epoxypropoxypheny1)dlethylrnethane 2, 506, 486

01-1 (O H1) (O EhOHh. Di(epoxypropoxyphenyl)methylprqpylmethan 2, 506, 486

CHaC (CsHs) (CQHAOHh. Di(epoxypropoxyphenybmethylphenylmethane 2, 506, 486 C HC(GeH5) (CeH4OHh Di(epoxypropoxyphonyl)ethylphenylmethane 2, 506, 486 C H1G(CaH5) (C6H4OH): Di(epoxypropoxyphonyl)propylphenylmethane 2, 506, 486 CiHgCwuH (C PhOHhH "D1(epoxypropoxyphenyl)butylphenylmethane 2, 506, 486

(011 0 114) CH(C5H4OH):... DKepoxypropoxyphenyl)tolylrnethane t. 2, 506, 486

( CH O H C (CH 05 34011. Di(epoxypropoxyphenyl)tolylmethylmethan 2, 506, 486

Dihydroxy diphenyl 4,4-bis(2,3-epoxypropoxy)diphenyl 2,530,353 (OH3)C(O4H5.COH3OH)2 2,2-bis(4-(2,3-epoxypropoxy)Z-tertiarybutylphenyDprop 2, 530, 353

phenols, which are sometimes referred to as diglycidyl Subdivision B ethers, have been described in a number of patents. For As to the preparation f low..molal polymeric epoxides convenience, reference will be made to two only, to wit, or mixtures referance i made to af ti d S. aforementioned U. S. Patent 2,506,486, and aforemen- Patents NOS, 2 575 nd 2 532 981 tioned U. S. Pa nt N In light of U. S. Patent No. 2,575,558, the following Purely y y Of illustration, the followlng 116190711668, examples can be specified by reference to the formula therein provided one still bears in mind it is in essence an over-simplification.

TABLE II i C-CC ORi[. ]-RiO-C--C--C- j ORi-[R].-R1OC-C-C H: H H1 Ha I H: H: H H:

OH n

(in which the characters have their previous significance) Example R Otrom HRlOH -R-- n 1: Remarks number B1 Hydroxy benzene CH: 1 0,1,2 Phenol kI0W!1 8.S bis-phenol A. Low polymeric mixture about or more where 11=0, remainder largely where I n=1, some where 7::2. CH:

122.. do.' j CH; 1 0,1,2 Phenol known asbis-phenolB. See note I (g regarding B1 above.

I (3H1 CH:

33 Orthobutylphenol CH: 1 0,1,2 Even though 1: is preferably 0, yet the l usual reaction product might well con- C tam materials where 'Il' is 1, or to a lesser degree 2. CH:

B4 Orthoamylphenol (I111: 1 0,1,2 Do.

Orthooctylphenol (IJH; 1 0,1,2 Do,

B6. Orthononylphenol (I311: 1 0,1,2 Do.

B7 Orthododecylphenol (EH: 1 I 0, 1,2 1 130.

" B8 Metacresol CH| 1 0,1,2 See prior note. This phenol used as in tial material is known as bis-phenol C. For other suitable bis-phenols see (I)H U. 8; Patent 2,564,191.

TABLE 11 (continued) Example R;O- from HR H -R- n n Remarks number B9 .do IfHs. 1 0,1,2 See prior note.

. c. +11: CH:

1310 Dibutyl (ortho-para) phenol. g 1 0,1,2 Do.

B11 Diamyl (ortho-para) phenol- 1 0,1,2 Do.

B12 Dioctyl (ortho-para) phenol. 1 0,1,2 Do.

1313 Dinonyl(ortho-para) phenol- 1g 1 D0.

B14-- Diamyl (ortho-para) phenol. 1% 1 0, 1, 2 Do.

| V CH:

B15 --do H 1 O, 1, 2 D0.

B16 Hydroxy benzene (I) 1 0,1,2 D0.

1317 Diamyi phenol (ortho-para). SS-- 1 0,1,2 Do.

B18- do -S; 1 0,1,2 Do I B19 Dibutylphenol(ortho-pam)- g g 1 0,1,2 Do.

B20 ..d0 H H 1 0,1,2 D0.

I I I 11 B21 Dinonylphenoi(ortho-para). 1g 1g 1 0,1,2 Do.

3822--.-.- Hydroxy benzene 0 1 0,1,2 Do.

B23....... -..--.d0 .Q None 0 0,1,2 D0.

B24 Ortho-isopropyl phenol CH; 1 0,1,2 See prior note. As to preparation 014,4-

I isopropylidene bis-(2-isopropyipheno1) see U. 8. Patent No. 2,482,748, dated 1 Sept. 21, 1949, to Dietzier. CH:

B25 Para-act l henol -CH B -GH 1 0,1 2 See rior note. (As to preparation of the y p r- 1 pli enol sulfide see U. S. Patent No. 2,488,134, dated Nov. 15, 1949, to Mikeska et a1.) B26 Hydroxybenzene" --1 a CH; 1 0,1,2 See prior note. (As to preparation olthe phenol sulfide see U. S. Patent No.

JHHI

Subdivision C The prior examples have been limited largely to those in which there is no divalent linking radical, as in the case of diphenyl compounds, or where the linking radical cyclic group such as the phenyl group or cyclohexyl group as in the instance of cyclohexylphenol or phenylphcnol. Such substituents are usually in the ortho position and may be illustrated by a phenol of the following composition:

13 Similar phenols which are monofunctional, for instance, paraphenyl phenol or paracyclohexyl phenol with an additional substituent in the ortho position, may be employed in reactions previously referred to, for instance, with formaldehyde or sulfur chlorides to give comparable phenolic compounds having 2 hydroxyls and suitable for subsequent reaction with epichlorohydrin, etc.

Other samples include:

OH OH CH3 CH3 wherein R1 is a substituent selected from the class consisting of secondary butyl and tertiary butyl groups and R2 is a substituent selected from the class consisting of alkyl, cycloalkyl, aryl, aralkyl, and alkaryl groups, and wherein said alkyl group contains at least 3 carbon atoms. See U. S. Patent No. 2,515,907.

in which the --C5H11 groups are secondary amyl groups. See U. S. Patent No. 2,504,064.

CeHia CoHu See U. S. Patent No. 2,285,563.

wherein R is a member of the group consisting of alkyl, and alkoxyalkyl radicals containing from 1 to 5' carbon atoms, inclusive, and aryl and chloraryl radicals of the benzene series. See U. S. Patent No. 2,526,545.

OH OH l a 1 E 1 CH; CH:

wherein R1 is a substituent selected from. the class consisting of secondary butyl and tertiary butyl groups and R2 is a substituent selected from the class consisting of alkyl, cycloalkyl, aryl, aralkyl, and alkaryl groups. See U. S. Patent No. 2,515,906.

See U. S. Patent No. 2,515,908.

As to sulfides, the following compound is of interest:

Q Q OH OH See U. S. Patent No. 2,331,448.

As to descriptions of various suitable phenol sulfides, reference is made to the following patents: U. S. Patents Nos. 2,246,321, 2,207,719, 2,174,248, 2,139,766, 2,244,- 021, and 2,195,539.

As to sulfones, see U. S. Patent No. 2,122,958.

As to suitable compounds obtained by the use of form-' aldehyde or some other aldehyde, particularly compounds such as Alkyl Alkyl Alkyl Alkyl in which R5 is a methylene radical, or a substituted methylene radical which represents the residue of an aldehyde and is preferably the unsubstituted methylene radical derived from formaldehyde. See U. S. Patent No. 2,430,002.

See also U. S. Patent No. 2,581,919 which describes di(dialkyl cresol) sulfides which include the monosulfides, the disulfides, and the polysulfides. The following formula represents the various dicresol sulfides of this invention:

OH OH: OH: OH

in which R1 and R2 are alkyl groups, the sum of Whose carbon atoms equals 6 to about 20, and R1 and R2 each preferably contain 3 to about 10 carbon atoms, and x is 1 to 4. The term sulfides as used in this text, therefore, includes monosulfide, disulfide, and polysulfides.

PART 4 It is well known that one can readily purchase on the open market, or prepare, fusible, organic solventsoluble, water-insoluble resin polymers of a composition approximated in an idealized form by the formula In the above formula n represents a small whole number varying from 1 to 6, 7 or 8, or more, up to probably 10 or 12 units, particularly when the resin is subjected to heating under a vacuum as desired in the literature.

from formaldehyde it may, of course, be derived from any other reactive aldehyde having 8 carbon atoms or less.

Because a resin is organic solvent-soluble does not mean it is necessarily soluble in any organic solvent. This is particularly true where the resinsare derived from trifunctional phenols as previously noted. However, even when obtained from a difunc'tional phenol, for instance paraphenylphenol, one may obtain a resin which is not soluble in a nonoxygenated solvent, such asbenzene, or xylene, but requires an oxygenated solvent such as a low molal alcohol, dioxane, or diethyleneglycol diethylether. Sometimes a mixture of the two solvents (oxygenated and nonoxygenated) will serve. See Example 9a of U. S. Patent No. 2,499,365, dated March 7, 1950, to De Groote' and Keisen. I

The resins herein employedas raw materials must be soluble in a nonoxygenated solvent, such as benzene or.

xylene. This presents no problem insofar that all that is required is to make a solubility test on commercially available resins, or else prepare resins which are xylene or benzene-soluble as described in aforementioned U. S- Patent No. 2,499,365, or in U. S. Patent No. 2,499,368, dated March 7, 1950 to De Groote and Keiser. In said patent there are described oxyalkylanon-susceptible, fusible, nonoxygenalted-o-rganic solvent-soluble, water-insoluble, low-stage phenolaldehyde resins having an average molecular weight corresponding teat least 3 and not over 6 phenolic nuclei per resin molecule. These resins are difunctional only in regard to methylol-formingjreactivity, are derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol, and are formed in the substantial absence of trifunctional phenols. The phenol is of the formula in which R is an aliphatic hydrocarbon radical having at least 4 carbon atoms and not more than 24 carbon atoms, and substituted in the 2,4,6 position.

If one selected a resin of the kind just described previously and reacted approximately one mole of the resin with two moles of formaldehyde and two moles ,of a basic nonhydroxylated secondary amine as'specified, following the same idealized over-simplification previously referred to, the resultant product might be illustrated thus:

The basic nonhydroxylated amine may be designed thus:

In conducting reactions of this kind one does not necesin the reactionproduct, as indicated in the following sarilyobtain a'hundredpercent yield for obvious reasons: Certainside reactions may take place. For instance, 2 moles of amine may combine with one mole of the aldehyde, or only one mole of the amine may combine with the resin molecule, or even to a very slight extent, if at all, 2 resin units may combine without auyamine unit goes one can use a mole of aldehyde other than formaldehyde, such as acetaldehyde, propionaldehyde or butyraldehyde. The resin unit may be exemplified thus:

in which R is the divalent radical obtained from. the particular aldehyde employed to form the resin. For reasons which are obvious the condensation product obtained appears to be described best in terms of the method of manufacture.

As previously stated the preparation of resins, the kind herein employedas reactants, is Well known. See 'previously mentioned U. S. Patent 2,499,368. Resins can be made using an acid catalyst or basic catalyst or a catalyst having neither acid nor basic properties in the ordinary sense or without any catalyst at all. It is preferable that the resins employed be substantially neutral. In other words, if prepared 'by using a strong acid as a catalyst, such strong acid should be neutralized. Similarly, if a strong base is used as a catalyst it is preferable that the base be neutralized although we have found that sometimes the reaction described proceeded more rapidly in the presence of a small amount of a free base. The

amount may be as small as a 200th of a percent and as much as a few 10ths of a percent. Sometimes moderate increase in caustic soda and caustic potash may be used. Howeve-r, the most desirable procedure in practically every case is to have the resin neutral.

In preparing resins'onedoes not get a single polymer, i. e one having just 3 units, or 'just 4 units, or just 5 units, or just 6 units, etc. It is usually a mixture; for instance, one approximating .4 phenolic nuceli will have some trimer and pentamer'prescnt. Thus, the molecular weight maybe such that it corresponds to a fractional value for n as, for example, 3.5, 4.5 or 5.2.

In theactual manufacturev of the resins we found no reason forusing other than those which are lowest in price and most readily available commercially. For purposes .of convenience suitable resins are characterized in the following table:

TABLEIII Mol. wt. Ex- R of resin ample R Position derived a molecule number of R from- (based on n+2) Phenyl Para. i Formal- 3. 5 992. 5

dehyde. Tertiary butyl. do 3. 5 882. 5 Secondary butyl 3. 5 882.5 Cycl-hexyl 3. 1,025. 5 Tertiary amyl .do 3. 5 959. 5 Mixed secondary Ortl1o 3:5 805. 5

and tertiaryamyl. Pro yl Para. 3. 5 805. 5 Tertiary hexyl 3. 5 '1, 036. 5 Octyl 3. 5 1, 190. 5 3. 5 1, 267. 5 3. 5 1, 344. 5 3. 5 1, 498. 5 Tertiary butyl 3. 5 945. 5

Tertiary amyl 3. 5 1, 022.5 Nonyl 3. 5 1, 330. 5 Tertiary butyl 3. 5 1, 071.5

Tertiary amyl 3. 5 1, 148.5 Nonyl 3. 5 1, 456. 5 Tertiary butyl 3. 5 1, 008. 5

Tertiary amyl 3. 5 1,085. 5 Nonyl 3. 5 1, 393. 5 Tertiary butyl. 4. 2 996. 6

4. 2 1, 083. 4 4. 2 1, 430. 6 4. 8 1,094.4 4. 8 l, 189. 6 4. 8 1, 570. 4 1. 5 604. 0 Oycl0-hexy1- 1.5 646. O Hexyl" 1. 5 653. 0 1. 5 688. 0

2. 0 692.0 Hexyl 2.0 748. 0 Cyclo-hexyl 2. O 740. 0

PART 5 As has been pointed out previously, the amine herein employed as a reactant is a basic secondary monamine, and preferably a strongly basic secondary m-onamine, free from hydroxyl groups whose composition is indicated thus:

in which R represents a monovalent alkyl, alicyclic, arylalkyl radical and may be heterocyclic in a few instances as in the case of piperidine and a secondary amine derived from furfurylamine by methylation or ethylation, or a similar procedure.

Another exampl of a heterocyclic amine is, of course, morpholine.

The secondary amines most readily available are, of course, amines such as dimethylamine methylethylamine, diethylamine, dipropylamine, ethylpropylamine, dibutylamine, diamulamine dihexylamine, dioctylamine, and dinonylamine. Other amines include his (1,3dimethylbutyl)amine. There are, of course, a variety of primary amines which can be reacted with an alkylating agent such as dimethyl sulfate, diethyl sulfate, an alkyl bromide, an ester of sulfonic acid, etc., to produce suitable amines Within the herein specified limitations. For example, one

can methylate alpha-methyl-benzylamine, or benzylamine itself, to produce a-suitable reactant. Needless'to say, one can use secondary amines suchas dicyclohexylamine, dibutylamine or amines containing one cyclohexyl group and one alkyl group, or one benzyl group and one alkyl group, such as ethylcyclohexyl amine, ethyl-benzylamine, etc.

Another class of amines which are particularly desirable for the reason that'they introduce a definite hydrophile effect by virtue of an ether linkage, or repetitous ether linkage, are certain-basic polyether amines of the formula in which x is a small whole number having a value of 1 or more and may be as much-as 10 or 12; n-is an integer having'a valu of 2 to 4, inclusive; m represents the numeral l to 2; and m represents a number 0 to 1, with the proviso that the sum of m plus in equals 2; and R has its prior significance, particularly as a hydrocarbon radical.

The preparation of such amines has been described in the literature and particularly in two United States patents, to wit, U. S. Nos. 2,325,514, dated July 27, 1943, to

Hester, and 2,355,337, dated August-8, 1944, to Spence.

The latter patent describes: typicalhaloalkyl ethers such as CHSO CaHtCl CHz--CH2 C Ha C HC H10 021140 CJHIBI'.

Such haloalkyl ethers can react with ammonia, or with a. primary amine such as methylamine, ethylamine, cyclohexylamine, etc., to produce a secondary amine of the kind above described, in which one of the groups attached to nitrogen is typified'by 'R. Such haloalkyl ethers also can be reacted with ammonia to give secondary amines as described in the first of the two patents mentioned immediately preceding. Compounds so obtained are exemplified by (031140 C7H4O CQHOgNH aHr'IO 61114 021140 C: 4) :NH

(C4Hc0 CH:CH(CH3)'O (CH3) CHCHEMNH (CHaO CHzCHzO CHzCHaO CHzCHahNH (CHaOCHaCHaCHzCHzCHiMNH Other somewhat similar secondary amines are those of the composition art san:

719 as'described'in U. S. Patent No. 2,375,659, dated May 8, 1945, to Joneset al. In the above formula R may be methyl, ethyl, propyl, amyl, octyl, etc.

Other amines can be obtained from products which are sold in theopen market, such as may be obtained by alkylation of, cyclohexylmethylamine or the alkylation of similar primary amines, or, for that matter, amines of the kind'described in U. S. Patent No. 2,482,546, dated September 20, 1949, to Kaszuba provided there is no negative group or halogen attached to the phenolic nucleus. Examples include the following: beta-phenoxyethylamine, gamma-phenoxypropylamine, beta-phenoxy-alpha-methylethylamine, and beta-phenoxypropylamine.

Other suitable amines are the kind described in British Patent No. 456,517 and may be illustrated by:

PART 6 The products obtained by the herein described processes employed in the manufacture of the condensation product represent cogeneric mixtures which are the result of a com densation reaction or reactions. Since the resin molecular cannot be defined satisfactorily by formula, although it may be so illustrated in an idealized simplification, it is diflicult to actually depict the finalproduct of the c'ogeneric mixture except in terms of the process itself.

Previous reference has been made to the .fact. that the procedure herein employed is comparable, in a general way, tothat 'which corresponds to somewhat similar d6? rivatives made either from phenols as differentiated from a resin, or in the manufacture of a phenol-amine-aldehyde resin; or else from a particularly selected resin and an amine and formaldehyde in the manner described in Bruson Patent No. 2,031,557, in order to obtain a heatreactive resin. Since the condensation products obtained are not heat-convertible and since manufacture is not restricted to a single phase system, and since temperatures up to 150 C. or thereaboutsmay be employed, it is obvious that the procedure becomes comparatively simple. Indeed perhaps no description is necessary over and above what has been said previously, in light of subsequent ex-. amples. However, for purpose of clarity the following details are included. v: n i j A convenient piece of equipmentforpreparation of these cogeneric mixtures is ,a resin pot of thekind described in aforementioned U. S Patent No. 2,499,368. In most instances the resin selected is: not apt to be a fusible liquid at the early or low temperature stageof reaction if employed assubsequently described; in fact, usu-v ally it is apt to be -a solid at ordinary or higher temperatures for instance, ordinary room temperature. Thus, we have found it convenient to use a solvent and particularly one which can be removed readily at a comparatively moderate temperature, for instance, at 150 C. A suitable solvent is usually benzene, xylene, or a comparable petroleum hydrocarbon or a mixture of such or similar solvents. Indeed, resins which are not soluble except in oxygenated solvents or mixtures containing such solvents are not here included as raw materials. The reaction can be conducted in such a way that the initial reaction, and perhaps the bulk of the reaction, takes place in a polyphase system. However, if desirable, one can use an oxygenated solvent' such as. a low-boiling? alcohol; including ethyl alcohol, methyl alcohol, etc.-::-.Higher alcohols can be used or one can use a comparatively non-volatile solvent such as dioxane or the diethylether of ethyleneglycol. One can also use a mixture of benzene or xylene and such oxygenated solvents. Note that the use of such oxygenated solvent is not required in the sense that it is not necessary to use an initial resin which is soluble only quently and makes it easier to prevent any loss.

30% formaldehyde. However, paraformaldehyde can be used but it is more difficult perhaps to add a solid mate rial instead of the liquid solution and, everything else being equal, the latter is apt to be more economical. In-

any event, water is presentas water of reaction. If the solvent is completely removed'at the end of the process, no problem is involved if the material is used for any subsequent reaction. .However if the reactionmass is I going to be subjected to some furtherreaction where the solvent may be objectionable, as in the case of ethyl or hexyl alcohol, and if there is to be subsequent oxyalkyla-.

tion, then, obviously, the alcohol should not be used or else it should be removed. Thefact that an oxygenated solvent need not lie-employed, of course, is an advantage for reasons stated.

The products obtained, depending on the reactants selected, may be water-insoluble or water-dispersible, or water-soluble, or close to being water-soluble. Water solubility is enhanced, "of course, by making a solution in the acidified vehicle such as a dilute solution, for instance, a 5% solution of hydrochloric acid, acetic acid, hydroxyacetic acid, etc. One also may convert the finished product into salts by simply adding a stoichiometric amount ofany selected acid and removing any water present by 'refluxingwith benzene or the like.

We have found no particular advantage in using a low temperature in the early stage of the reaction because, and for reasons explained, this is not necessary although it does apply in some other procedures that, in a general way, bear some similarity to the present procedure. There is no objection, of course, to giving the'reaction an opportunity to proceed as far as it will at some low temperature, for instance, 30 to 40 but ultimately one must employ the higher temperature in order to obtain products of the kind herein described. temperature reaction is used initially the period is not critical, in fact, it maybe anything from a few hours up to 24 hours. We have not found any case where it was necessary or even desirable to hold the low temperature stage for more than 24 hours. In fact, we are'not convinced there is any'advantage in holding it at this stage for more than 3 or 4 hours at the most. This, again, is a matter of convenience largely for one reason. In heating and stirring the reaction mass there is a tendency for formaldehyde to be lost. Thus, if the reaction can be conducted at a lower temperature so as to use up part of the formaldehyde at such lower temperature, then the amount of unreacted form-aldehyde is decreased subse- Here, again, this lower temperature is not necessary by virtue of heat convertibility as previously referred to.

If solvents and reactants are selected so the reactants and products of reaction are mutually soluble, then agitation is required only to the extent that it'helps cooling or helps distribution of the incoming formaldehyde. This mutual solubility is not necessary as previously pointed out but may be convenient under certain circumstances. On the other hand, if the products are not mutually soluble then agitation should be more vigorous for the reason that. reaction probably takes place principally at the interfaceand the more vigorous the agitation the more interfacial=area. The general procedure employed is invariably the same when adding the resin and the selected solvent, such as benzene or xylene. Refluxing should be long' enough'to insure that the resin added preferably in a'powd ered form, is completely dissolved. However, if the "resin is'prepare'd as such it may beadded in solution form, "just as preparation is described in aforementioned If a lower U. S. Patent 2,499,368. After the resin is in complete solution the amine is added and stirred. Depending on the amine selected, it may or may not be soluble in the resin solution. If it is not soluble in the resin solution it may be soluble in the aqueous formaldehyde solution. If so, the resin then will dissolve in the formaldehyde solution as added, and if not, it is even possible that the initial reaction mass could be a three-phase system instead of a two-phase system although this would be extremely unusual. This solution, or mechanical mixture, if not completely soluble is cooled to at least the reaction temperature or somewhat below, for example 35 C. or slightly lower, provided this initial low temperature stage is employed. The formaldehyde is then added in a suitable form. For reasons pointed out we prefer to use a solution and whether to use a commercial 37% concentration is simply a matter of choice. In large scale manufacturing there may be some advantage in using a 30% solution of formaldehyde but apparently this is not true on a small laboratory scale or pilot plant scale. 30% formaldehyde may tend to decrease any formaldehyde loss or make it easier to control unreacted formaldehyde loss.

On a large scale if there is any difficulty with formaldehyde loss control, one can use a more dilute form of formaldehyde, for instance, a 30% solution. The reaction can be conducted in an autoclave and no attempt made to remove water until the reaction is over. Generally speaking, such a procedure is much less satisfactory for a number of reasons. For example, the reaction does not seem to go to completion, foaming takes place, and other mechanical or chemical difficulties are involved. We have found no advantage in using solid formaldehyde because even here water of reaction is formed.

Returning again to the preferred method of reaction and particularly from the standpoint of laboratory procedure employing a glass resin pot, when the reaction has proceeded as far as one can reasonably expect at a low temperature; for instance, after holding the reaction mass with or without stirring, depending on whether or not it is homogeneous, at 30 or 40 C. for 4 or 5 hours, or at the most, up to -24 hours, we then complete the reaction by raising the temperature up to 150 C., or thereabouts as required. The initial low temperature procedure can be eliminated or reduced to merely the shortest period of time which avoids loss of amine or formaldehyde. At a higher temperature we use a phaseseparating trap and subject the mixture to reflux condensation until the water of reaction and the water of solution 'of the formaldehyde is eliminated. We then permit the temperature to rise to somewhere about 100 C., and generally slightly above 100 C., and below 150 C., by eliminating the solvent or part of the solvent so the reaction mass stays within this predetermined range. This period of heating and refluxing, after the water is eliminated, is continued until the reaction mass is homogeneous and then for .one to three hours longer. The removal of the solvent-s is conducted in a conventional manner in the same way as the removal of solvents in resin manufacture as described in aforementioned U. S. Patent No. 2,499,368.

Needless to say, as far as the ratio of reactants goes we have invariably employed approximately one mole of the resin based on the molecular weight of the resin molecule, 2 moles of the secondary amine and 2 moles of formaldehyde. In some instances we have added a trace of caustic as an added catalyst but have found no particular advantage in this. In other cases we have used a slight excess of formaldehyde and again, have not found any particular advantage in this. In other cases we have used a slight excess of amine and again, have not found any particular advantage in so doing. Whenever feasible we have checked the completeness of reaction in the usual ways, including the amount of water 22 of reaction, molecular weight, and particularly in some instances have checked whether or not the end-product showed surface-activity, particularly in a dilute acetic acid solution. The nitrogen content after removal of unreacted amine, if any is present, is another index.

In light of what has been said previously, little more need be said as to the actual procedure employed for the preparation of the herein described condensation products. The following example will serve by way of illustration.

Example 1b The phenol-a1dehyde resin is the one that has been identified previously as Example 2a. It was obtained from a para-tertiary butylphenol and formaldehyde. The resin was prepared using an acid catalyst which was completely neutralized at the end of the reaction. The molecular weight of the resin was 882.5. This corresponded to an average of about 3 /2 phenolic nuclei, as the value for n which excludes the two external nuclei, i. e., the resin was largely a mixture having 3 nuclei and 4 nuclei, excluding the two external nuclei or 5 and 6 overall nuclei. The resin so obtained in a neutral state had a light amber color.

'882 grams of the resin identified as 2a, preceding, were powdered and mixed with an equal weight of xylene, i. e., 882 grams. The mixture was refluxed until solution was complete. It was then adjusted to approximately 30 C. to 35 C., and 146 grams of diethylamine added. The mixture was stirred vigorously and formaldehyde added slowly. The formaldehyde was used as a 37% solution and 1 62 grams were employed, which were added in about 2 /2 hours. The mixture was stirred vigorously and kept within a temperature range of 30 to 45 C. for about 20 hours. At the end of this period of time it was refluxed, using a phase-separating trap and a small amount of aqueous distillate withdrawn from time to time, and the presence of unreacted formaldehyde noted. Any unreacted formaldehyde seemed to disappear within 2 to 3 hours after refluxing was started. As soon as the odor of formaldehyde was no longer detectible the phaseseparating trap was set so as to eliminate .all water of solution and reaction. After the water was eliminated part of the xylene was removed until the temperature reached approximately C., or slightly higher. The mass was kept at this higher temperature for about 4 hours and reaction stopped. During this time any addition-al water, which was probably water of reaction which had formed, was eliminated by means of the trap. The residual xylene was permitted to stay in the cogeneric mixture. A small amount of the sample was heated on a water bath to remove the excess xylene and the residual material was dark red in color and had the consistency of a sticky fluid or tacky resin. The overall time for the reaction was about 30 hours. Time can be reduced by cutting low temperature period to approximately 3 to 6 hours.

Note that in Table IV following there are a large number of added examples illustrating the same procedure. In each case the initial mixture was stirred and held at a fairly low temperature (30 to 40 C.) for a period of several hours. Then refluxing was employed until the odor of formaldehyde disappeared. After the odor of formaldehyde disappeared the phase-separating trap was employed to separate out all the water, both the solution and condensation. After all the water had been separated enough xylene was taken out to have the final product reflux for several hours somewhere in the range of 145 to 150 C., or therea'bouts. Usually the mixture yielded a clear solution by the time the bulk of the water or all of the water, had been removed.

Note that as pointed out previously, this procedure is illustrated by 24 examples in Table IV.

TABLE IV Strength of Reac- Reac- Max. Ex. Resin Amt, Amine used and amount formalde- Solvent used tion, tion distill No. used grs. hyde soln. and amt. temp. time, temp.,

V and amt. 0. hrs. 0.

S82 Dicthylamlne, 146 grams 37%, 162 g Xylene, 882 g--. 20-25 30 150 480 Diethylamine, 73 grams 37%, 81 g Xylene, 480 g.-. 22-30 24 152 633 do 30%, 100 g Xylene, 633 g.-. 21-24 38 147 441 Dibutylamine, 129 grams..." 37%, 81 g Xylene, 441 g 25-37 32 149 480 .do 1 1 do Xylene, 480 g-.. 20-24 35 149 633 .do 1 Xylene, 633 g-. 18-23 24 150 882 Morpholine, 174 grams 37%, 162 g... Xylene, 882 g. 20-26 35 145 480 Morpholine, 87 grams. 37%, Xylene, 480 g- 19-27 24 156 633 .do d Xylene, 633 g 20-23 24 147 473 Dioctylamine (6.1-2 100 Xylene, 473 g 20-21 38 143 511 o d Xylene, 511 g 19-20 30 145 665 do 37%, Xylene, 665 g 20-26 24 150 441 (O HOC2H OC2H9zNH, 250 grams 30%, 100 g... Xylene, 441 g.-. 20-22 31 147 480 (0 11 0 O2H4OC2H-l)2NH, 250 grams... d Xylene, 480 g" 20-24 36 148 595 (CZG5002H4OCIH4)ZNH, 250 grams 37%, 81 g Xylene, 595 g. 23-28 25 145 441 (C4H0OCHZCH(OH3)0(GH3)CHCH2)2NH, 361 grams r Xylene, 441 g.-. 21-23 24 151 480 (C4H9OOH2CH(CH3)O(CH3)OHCH2)2NH, 361 grams do Xylene, 480 g 20-24 24 150 511 (0411900112011 CH3 O CH3 CHOH2 2NH, 361 grams 30%, 100 g Xylene, 511 g 20-22 25 140 498 (GHQOCHZCHZ CH2CHzOGHzGH2)zNH, 309 grams- 37%, 81 g Xylene, 498 g... 20-25 24 140 542 (CH3OCHZOHQO GHgOHzOGHZOH2)3NH, 309 grams. do Xylene, 542 g- 28-38 30 142 547 (01130011201120omomoomomnNH, 309 grams. do Xylene, 547 g 25-30 26 148 441 (C330CHQOHZCHZOH2OHZOH2 2NH 245 gramsdo Xylene, 441 g 20-22 28 143 595 (C11 0CHZCH CH OILCHZCHmNH, 245 grams 30%, 100 g-.. Xylene, 595 g--. 18-20 25 140 391 (CHBOCHZOHZOHQOHZCH2GH2)2NH, 98 grams 30%, 50 g Xylene, 391 g. 19-22 24 145 PART 7 In preparing oxyalkylated derivatives of products of the kind which appear as examples in Part 3, we have found it particularly advantageous to use laboratory equipment which permits continuous oxypropylation and oxycthylation. The oxyethylaition step is, of course, the same as the oxypropylation step insofar that two low boiling liquids are handled in each instance. The oxyalkylation step is carried out in a manner which is substantially conven-' tional for the oxyalkylation of compounds having labile hydrogen atoms, and for that reason a detailed description of the procedure is omitted and the process will simply be illustrated by the following examples:

Example The oxyalkylation-susceptible compound employedis the one previously described and designed asflExample 1b. Condensate 1b was in turn obtained from diethy-laminc and the resin previously identified Example 2a. Reference to Table III shows that this particular resin is obtained from paratertiary-butylphenol and formaldehyde. 10.56 pounds of this resin condensate-were dissolved in 8.8 pounds of solvent (xylene) along with one pound of finely powdered caustic soda as a catalyst. Adjustment was made in the autoclave 'to operate at a temperature of approximately 125 C. to 130 C., and at a pressure of about to pounds.

The time regulator was set so as to inject the ethylene oxide in approximately three hours and then continue stirring for a half-hour or longer. The reaction went readily and, as a matter of fact, the ethylene oxide could have been injected in less than an hours time and probably .the reaction could have been completed without allowing for a subsequent stirring period. The speed of reaction, particularly at the low pressure, undoubtedly was due in a large measure to excellent agitation and also to the comparatively high concentration of catalyst. The amount of ethylene oxide introduced was equal in weight to the initial condensation product, to wit, 10.56 pounds. This represented a molal ratio of 24 moles of ethylene oxide per mole of condensate.

The theoretical molecular weight at the end of the reaction period was 2112.- A comparatively small example, less than 50 grams, was withdrawn merely for examination as far as solubility or emulsifying power was concerned and also for thev purpose of making some tests on various oil-field emulsions. The amount withdrawn was so sin-all that no cognizance of this fact is included in the data, or subsequent data, or in the data presented in tabul-ar'forrn in subsequent Tables 3 and 4.

The size of the autoclave employed was -gallons." In

innumerable comparable oxyalkylations we have withdrawn a substantial portion at the end of each step and continued oxyalkylation on a partial residual sample. This was not the case in this particular series. Certain examples were duplicated as hereinafter noted and subjccted to oxyalkylation with a different oxide.

Example 20 This example simply illustrates the further oxyalkyla- .tion of Example 10, preceding. As previously stated, the oxyalliylation-susceptible compound, to wit Example-1b, present at the beginning of the stage Was obviously the same as at the'end of the prior stage (Example 10), to wit, 10.56 pounds. The amount of oxide present in the initial step was 10.56 pounds, the amount of catalyst remained the same, to wit, one pound, and the amount of solvent remained the same. was another 10.56 pounds, all addition of oxide in these various stages beingbased on the addition of this particular amount. Thus, at the end of the oxyethylation step the amount of oxide added was a total of 21.12 pounds and the molal ratio of ethylene oxide to resin condensate was 48 to l. The theoretical molecular weight was 3168.

The maximum temperature during the operation was C. to C. The maximum pressure was in the range of 15 to 20 pounds. The time period was 3% hours.

Example 30 The oxyalkylation proceeded in the same manner described in Examples 1c and 2c. There was no added solvent and no added catalyst. The oxide added was 10.56 pounds and the total oxide in at the end of the oxyethylation step was 31.68 pounds. The molal ratio of oxide to condensatewas 72 to 1. Conditions as far as temperature and pressure and time were concerned were all the same as in Examples 10 and 2c. The time period, as in Examples 1c and 2c, was 3 /2 hours.

Example 40 The oxyethylation was continued and the amount of oxide added again was 10.56 pounds. There was no added catalyst and no added solvent. The theoretical molecular weight at the end of the reaction period was 5 280. The molal ratio of oxide to condensate was 96 to 1. Conditions as far as temperature and pressure were concerned were the same as in previous examples. The time period was slightly longer, to wit, 4 hours. The reaction-unquestionably began to slow up somewhat.

The amount of oxide added.

25 Example 50 The oxyethylation continued with the introduction of another 10.56 pounds of ethylene oxide. No added solvent was introduced and, likewise, no added catalyst was introduced. The theoretical molecular weight at the end of the agitation period was 6336, and the molal ratio of oxide to resin condensate was 124 to 1. The time period, however, had increased to hours, even though the operating temperature and pressure remained the same as in previous example.

Example 66 The same procedure was followed as in the previous examples except that an added /4 pound of powdered caustic soda was introduced to speed up the reaction. The amount of oxide added was another 10.56 pounds, bringing the total oxide introduced to 63.36 pounds. The temperature and pressure during this period were the same as before.

Notwithstanding the addition of added caustic the time required for the oxyethylation was 5 hours. There was no added solvent.

Example 7c The same procedure Was followed as in the previous six examples without the addition of more caustic or more solvent. The total amount of oxide introduced at the end of the period was 72.93 pounds. The theoretical molecular weight at the end of the oxyalkylation period was 8448. The time required for the oxyethylation was a bit longer than in the previous step, to wit, 6 hours.

Example 80 This was the final oxyethylation in this particular series. There was no added solvent and no added catalyst. The total amount of oxide added at the end of this step was 85.48 pounds. The theoretical molecular weight was 9604. The molal ratio of oxide to resin condensate was 192. Conditions as far as temperature and pressure were concerned were the same as in the previous examples and the time required for oxyethylation was the same as in Example 70, preceding, to wit, 6 hours.

The same procedure as described in the previous examples was employed in connection with a number of the other condensates described previously. All these data have been presented in tabular form in a series of four tables, Tables V, VI, VII and VIII.

in substantially every case a 25-gallon autoclave was employed, although in some instances the initial oxyethylation was started in a I5-gallon autoclave and then transferred to a ZS-gallon autoclave. This is immaterial but happened to be a matter of convenience only. The solvent used in all cases was xylene. The catalyst used was finely powdered caustic soda.

Referring now to Tables V and VI, it will be noted that compounds 16 through 400 were obtained by the use of ethylene oxide, whereas 41c through 80c were obtained by the use of propylene oxide alone.

Thus, in reference to Table V it is to be noted as follows.

The example number of each compound is indicated in the first column.

The identity of the oxyalkylation-susceptible compound, to wit, the resin condensate, is indicated in the second column.

The amount of condensate is shown in the third column.

Assuming that ethylene oxide alone is employed, as happens to be the case in Examples 10 through 400, the amount of oxide present in the oxyalkylation derivative is shown in column 4, although in the initial step since no oxide is present there is a blank.

When ethylene oxide is used exclusively the 5th column is blank.

The 6th column shows the amount of powdered caustic soda used as a catalyst, and the 7th column shows the amount of solvent employed.

The 15th column shows the theoretical molecular weight at the end of the oxya'lkylation period.

The 8th column states the amount of condensate pres-' ent in the reaction mass at the end of the period.

As pointed out previously, in this particular series the amount of reaction mass withdrawn for examination was so small that it was ignored and for this reason the resin condensate in column 8 coincides with the figure in column 3.

Column 9 shows the amount of ethylene oxide employed in the reaction mass at the end of the particular period.

Column 10 can be ignored insofar that no propylene oxide was employed.

Column 11 shows the catalyst at the end of the reaction period.

Column 12 shows the amount of solvent at the end of the reaction period.

Column 13 shows the molal ratio of ethylene oxide to condensate.

Column 14 can be ignored for the reason that no propylene oxide was employed.

Referring now to Table VIII. It is to be noted that the first column refers to Examples 1c, 2c, 30, etc.

The second column gives the maximum temperature employed during the oxyalkylation step and the third column gives the maximum pressure.

The fourth column gives the time period employed.

The last three columns show solubility tests by shaking a small amount of the compound, including the solvent present, with several volumes of water, xylene and kerosene. It sometimes happens that although xylene in comparatively small amounts will dissolve in the concentrated material, when the concentrated material in turn is diluted with xylene separation takes place.

Referring to Table VI, Examples 410 through c are the counterparts of Examples 1c through 40c, except that the oxide employed is propylene oxide instead of ethylene oxide. Therefore, as explained previously, four columns are blank, to wit, columns 4 and 9.

Reference is now made to Table VII. It is to be noted these compounds are designated by d numbers, 1d, 2a, 3a, etc., through and including 32d. They are derived, in turn, from compounds in the 0 series, for example, 350, 39c, 53c and 620. These compounds involve the use of both ethylene oxide and propylene oxide. Since compounds 1c through 400 were obtained by the use of ethylene oxide, it is obvious that those obtained from 350, through 390, involve the use of ethylene oxide first, and propylene oxide afterward. Inversely, those compounds obtained from 530 and 620 obviously came from a prior series in which propylene oxide was used first.

In the preparation of this series indicated by the small letter d, as 1d, 2d, 3d, etc., the initial 0 series such as 350, 39c, 53c and 620, were duplicated and the oxyalkylation stopped at the point designated instead of being carried further as may have been the case in the original oxyalkylation step. Then oxyalkylation proceeded by using the second oxide as indicated by the previous explanation, to wit, propylene oxide in 1:] through 16d, and ethylene oxide in 170. through 32d, inclusive.

In examining the table beginning with ld, it will be noted that the initial product, i. e., 35c consisted of the 1 reaction product involving 10.5 pounds of the resin condensate, 15.84 pounds of ethylene oxide, 1.0 pound of caustic soda, and 8.8 pounds of the solvent.

It is to be noted that reference to the calalyst in Table VII refers to the total amount of catalyst, i. e., the catalyst present from the first oxyalkylation step plus added catalyst, if any. The same is true in regard to the sol- 27 vent. Reference to the solvent refers to the total solvent present, i. e., that from the first oxyalkylation step plus added solvent, if any.

In this series, it will be noted that the theoretical molecular weights are given prior to the oxyalkylation step and after the oxyalkylation step, although the value at the end of one step is the value at the beginning of the next step, except obviously at the very start the value depends on he theoretical molecular weight at theend of the initial oxyalkylation step; i. e., oxyethylation for 1d through 16d, and oxyp'ropylation for 17d through 32d. It .will be noted also the under the molal ratio the values of both oxides to the resin condensate are included.

The data given in regard to the operating conditions is substantially the same as before and appears in Table VIII.

The products resulting from these procedures may contain modest amounts, or have small amounts, of the solvents as indicated by the figures in the tables. If desired the solvent may be removed by distillation, and particularly vacuum distillation. Such distillation also may remove traces or small amounts of uncombined oxide, if present and volatile under the conditions employed.

Obviously, in the use of ethylene oxide and propylene oxide in combination one need not first use one oxide and then the other, but one can mix the two oxides and thus obtain what may be termed an indifferent oxyalkylation, i. e., no attempt to selectively add one and then the other, or any other variant.

Needless to say, one could start with ethylene oxide and then use propylene oxide, and then go back to ethylene oxide; or, inversely, start with propylene oxide, then use ethylene oxide, and then go back to propylene 28 oxide; or, one could use a combination in which butylene oxide is used along with either one of the two oxides just mentioned, or a combination of both of them..

The colors of the products usually vary from a reddish amber tint to a definitely red,'and amber. The reason is primarily that no effort is made to obtain colorless resins initially and the resins themselves may be yellow, amber, or even dark amber. Condensation of a nitrogenous product invariably yields a darker product than the original resin and usually has a reddish color. The solvent employed, if'xylene, adds nothing to the color but one may use a darker colored aromatic petroleurn solvent. Oxyalkylation generally tends to yield lighter colored products and the more oxide employed the lighter the color of the product. Products can be prepared in which the final color is a lighter amber with a reddish tint. Such products can be decolorized by the use of clays, bleaching chars, etc. As far as use in demulsification is concerned, or some other industrial uses, there is no justification for the cost of bleaching the product.

Generally speaking, the amount of alkaline catalyst present is comparatively small and it need not be removed. Since the products per se are alkaline due to the presence of a basic nitrogen, the removal of the alkaline catalyst is somewhat more ditficult than ordinarily is the case for the reason that if one adds hydrochloric acid, for example, to neutralize the alkalinity one maypartially neutralize the basic nitrogen radical also. The preferred procedure is to ignore the presence of the alkali unless it is objectionable or else add a stoichiometric amount of concentrated hydrochloric acid equal to the caustic soda present.

TABLE V Composition before Composition at end Molal ratio Molec. Ex. No. wt.

0-8 0-8 Ethl. Propl. Oata- Sol- O-S* Ethl. Propl. Cata- S01- Ethyl. Propl. based cmpd., cmpd., oxide, oxide, lyst, vent, cmpd., oxide, oxide, lyst, vent, oxide oxide on theex. N0. lbs. lbs. lbs. lbs. lbs. lbs. lbs. lbs. lbs. lbs. to oxyto oxyoretical alkyl. alkyl. value suscept. suscept. cmpd. cmpd.

1. 0 8. 8 10. 56 10. 56 1. 0 8. 8 1. 0 8. 8 10.56 21. 12 1. 0 8. 8 1. 0 8. 8 10. 56 31. 68 1. 0 8. 8 1. 0 8. 8 10. 56 42. 24 1. 0 8. 8 1. 0 8. 8 10. 56 52. 80 1. 0 8. 8 1.25 8.8 10.56 63.36 1.25 8.8 1. 25 8. 8 10. 56 73.92 1. 25 8. 8 1. 25 8. 8 10. 56 85.48 1. 25 8. 8 1. 0 9. 6 12.56 12. 56 1. 0 9. 6 1. 0 9. 6 12. 56 25. 12 1. 0 9. 6 1. 0 9. 6 12. 56 37. 68 1. 0 9.6 1. 0 9. 6 12. 56 50. 24 1. 0 r 9. 6 1. 0 9. 6 12. 56 62. 80 1. 0 9. 6 1. 5 9.6 12.56 75. 36 1. 5 9. 6 1. 5 9. 6 12. 56 87.92 1. 5 9. 6 1. 5 9. 6 12.56 100.48 1. 5 9.6 1.0 8. 8 10.84 10.84 1.0 8.8 1. 0 8. 8 10. 84 21. 68 1. 0 8. 8 1. 0 8. 8 10.84 32. 52 1. 0 8. 8 1. 0 8. 8 10.84 43. 36 1. 0 8. 8 1. 0 8. 8 10.84 54. 20 1. 0 8. 8 1. 25 8. 8 10. 84 65. O4 1. 25 8. 8 1. 25 8. 8 10. 84 75.88 1. 25 8. 8 1. 25 8. 8 10. 84 86. 72 1. 25 8. 8 1. 0 10.2 12.84 12. 84 1. 0 10. 2 1. 0 10.2 12. 84 25. 68 1. O 10. 2 1. 0 10.2 12. 84 38. 52 1. 0 10.2 1. 0 l0. 2 12.84 51. 36 1. 0 10. 2 1. 0 10. 2 12. 84 64. 20 1. 0 10. 2 1. 5 10. 2 12. 84 77. O4 1. 5 10. 2 1.5 10. 2 12. 84 89.88 1. 5 10.2 1. 5 10. 2 12. 84 102. 72 1. 5 10. 2 1. 0 8. 8 10. 56 5. 28 1. 0 8. 8 1. 0 8. 8 10. 56 10.56 1. 0 8. 8 1. 0 8. 8 10.56 15. 84 1. 0 8. 8 1.0 8.8 10.56 21.12 1.0 8.8 1. 0 8. 8 10.56 26. 1. 0 8. 8 1. 0 8. 8 10.56 31.68 1. 0 8. 8 1. 0 8. 8 10.56 36.96 1. 0 8. 8 1. 0 8. 8 10.56 42. 24 1. 0 8. 8

'Oxyalkylatlon-susoeptible.

TABLE VI Composition before Composition at end Molal ratio Molee. Ex. No. wt.

-5 0-8 Ethl. Propl. Cata- Sol- O=S* Ethl; Prop]. Cata- Sol- Ethyl. Propl. based empd., empd., oxide, oxide, lyst, vent, empd., oxide, oxide, lyst, vent, oxide oxide on theex. No. lbs. lbs. lbs. lbs. lbs. lbs. lbs. lbs. lbs. lbs. to oxyto oxyoretical alkyl. alkyl. value suscept. suscept. cmpd. cmpd.

41c.... 1.0 8.8 10.56 10. 56 1.0 8. 8 18.2 2, 112 1. 0 8. 8 10.56 21.12 1. 0 8. 8 36.4 3,168 1. 0 8. 8 10.56 21. 68 1. 0 8. 8 54.6 4, 224 1. 0 8. 8 10. 56 42. 24 1. 0 8.8 72. 8 5, 280 1. 0 8. 8 10. 56 52. 80 1. 0 8. 8 91.0 6, 336 1. 8.8 10.56 73. 92 1. 5 8. 8 127. 4 8, 348 1. 5 8. 8 10.56 95.04 1. 5 8. 8 163. 8 10, 560 1. 5 8.8 10.56 116.16 1.5 8. 8 200. 2 12, 672 1.2 9. 6 12.56 12. 56 1. 2 9. 6 21.6 2, 512 1.2 9. 6 12.56 25.12 1.2 9. 6 43.2 3,768 1. 2 9. 6 12.56 37. 68 1. 2 9. 6 64. 8 5,024 1. 2 9. 6 12. 56 50. 24 1. 2 9. 6 86. 4 6,280 1. 2 9. 6 12.56 62. 80 1. 2 9. 6 108.0 7, 836 1. 2 9. 6 12.56 87.92 1. 2 9. 6 151. 2 10,048 1. 2 9. 6 12.56 113.04 1. 2 9. 6 194. 8 12, 560 1. 2 9. 6 12.56 138.16 1.2 9. 6 238. 2 15, 072 1. 0 8. 8 10.84 10.84 1. 0 8.8 18.7 2, 168 1. 0 8.8 10.84 21. 68 1.0 8. 8 37. 4 3, 252 1. 0 8. 8 10.84 32. 52 1. 0 8. 8 56.1 4, 336 1. 0 8.8 10. 84 43. 36 1. 0 8. 8 74. 8 5, 420 1. 0 8. 8 10.84 54. 1. 0 8. 8 93. 5 6, 504 1. 0 8. 8 10.84 75. 88 1.0 8. 8 130.9 8, 672 1. 0 8. 8 10.84 97. 56 1. 0 8. 8 170. 3 10,840 1. 0 8. 8 10.84 119. 24 1. 0 8. 8 205. 7 13, 008 1. 0 10.2 12.84 12. 84 6 10.2 22. 2 2, 568 1. 0 10.2 12.84 25. 68 .6 10.2 44. 3 3, 852 1. 0 10.2 12. 84 38. 52 .6 10.2 66. 4 5,136 1. 0 10. 2 12.84 51. 36 .6 10.2 88. 5 6, 420 1. 0 10.2 12.84 64. 20 .6 10.2 110.6 7, 704 1.25 10.2 12.84 89. 88 .9 10.2 154. 8 10, 272 1. 25 10. 2 12. 84 115. 56 .9 l0. 2 199.5 12, 840 1. 25 10. 2 12. 84 141. 24 9 10.2 244. 0 15, 408 1.0 8.8 10.56 5.28 1.0 8.8 9.1 1, 584 1. 0 8.8 10. 56 10.56 1. O 8. 8 18. 2 2,112 1. 0 8.8 10. 56 15. 84 1. 0 8.8 27. 3 2, 640 1.0 8. 8 10. 56 21.12 1. 0 8. 8 .1 36.4 3,168 1. 0 8.8 10. 56. 26. 1. 0 8.8 45.5 3, 696 1. 0 8. 8 10. 56 36.96 1. 0 8. 8 63.7 4, 752 1.05 8. 8 10. 56' 47.52 1. 25 8.8 81. 9 5,805 1. 25 8. 8 10. 56 58. 08 1.25 8. 8 100. 1 6, 864

*Oxyalkylation-susceptible.

TABLE VII Composition before Composition at end Molal ratio Molec. Ex. No. Wt.

OS* 0-8 Ethl. Propl. Cata- Sol- 0 8'? Ethl. Propl. Cata- Sol- Ethyl. Propl. based cmpcL, cmpd., oxide, oxide, lyst, vent, cmpdc, oxide, oxide, lyst, vent, oxide oxide on theex. N 0. lbs. lbs. lbs. lbs. lbs. lbs. lbs. lbs. lbs. lbs. to ox,vto oxyoretical alkyl. alkyl. value suscept. suscept. cmpd. cmpd.

10. 56 15. 84 1. 0 8. 8 10. 56. 15; 84 5. 28 1. 0 S. 8 36 9. 1 3, 168 10.56 15.84 5.28 1. 0 8. 8 10. 56 15.84 10.56 1. 0 8. 8 36 18. 2 3, 696 10.56 15. 84 10. 56 1. 0 8. 8 10. 56 15; 84 15.84 1. 0 8.8 36 27. 3 4, 224 10. 56 15.84 15. 84 1. 0 8. 8 10. 56 15. 84 21. 12 1. 0 8. 8 36 36.4 4, 752 10. 56 15.84 21. 12 1. 5 8. 8 10.56. 15. 84 26.40 1. 5 8. 8 36 45. 5 5, 380 10.56 15.84 26. 40 1. 5 8. 8 10. 56 15.84 31.68 1.5 8. 8 36 54.6 5, 908 10. 56 15. 84 31. 68 1. 5 8. 8 10 5,6 15. 84 36. 96 1. 5 8. 8 36 63. 7 6, 438 10. 56 15. 84 36. 96 l. 5 8. 8 10. 56 15. 84 42. 24 l. 5 8. 8 36 72. 8 6, 964 10.56 36. 96 1. 5 8. 8 10,56 36. 96 5. 28 1. 5 8.8 84 9.1 5, 280 10. 56 36. 96 5. 28 1. 5 8. 8 10. 56 36. 96 10. 56 l. 5 8. 8 84 18. 2 5, 808 36.96 10. 56 1. 5 8.8 10. 56, 36. 96 15. 84 1. 5 8.8 84 27.3 6, 336 15. 84 1. 5 8. 8 10, 56 36. 96 26. 40 1. 5 S. 8 84 45. 5 7, 392 26. 40 1. 5 8. 8 10. 56 36. 96 36. 96 1. 5 8. 8 84 63. 7 8, 448 36. 96 1. 5 8. 8 10:56 36. 96 47. 52 l. 5 8. 8 84 81. 9 9, 504 47. 52 l. 5 8. 8 10. 56 36. 96 58. 08 1. 5 8. 8 84 100. 1 10, 560 58.08 1. 5 8. 8 10.56 36. 96 68. 64 1.5 8. 8 84 118. 3 11,616 62. 1. 8 9. 6 12. 56 6. 28 62. 80 1. 7 9. 6 14. 3 108. 0 8, 468 62. 80 1. 7 9. 6 12. 56 12. 56 62.80 1. 7 9. 6 28. 6 108. 0 9, 092 62.80 1. 7 9. 6 12. 56 18. 84 62.80 1. 7 9. 6 42. 8 109. 0 10, 348 62.80 1. 7 9. 6 12.56 31. 40 62.80 1. 7 9. 6 71. 4 108.0 604 62. 80 1. 7 9. 6 12. 56 43. 96 62. 80 1. 7 9. 6 99. 9 108. 0 12, 860 62. 80 1. 7 9. 6 12. 56 56. 52 62.80 1. 7 9. 6 128. 5 108. 0 14, 116 62. 80 1. 7 9. 6 12. 56 69. 08 62. 80 1. 7 9. 6 157. 0 108. 0 15, 372 62. 80 1. 7 9. 6 12. 56 81. 64 62. 80 l. 7 9. 6 185. 8 108. 0 16, 628 75. S8 1. 5 8. 8 10. 84 5. 42 75. 88 l. 5 8. 8 12. 3 130. 9 9, 214 10. 84 75. 88 1. 5 8. 8 10. 84 10.84 75. 88 1. 5 8. 8 24. 6 130. 9 9, 756 10. 84 75.88 1. 5 8. 8 10. 84 16. 26 75. 88 l. 5 8. 8 36. 9 130. 9 10, 298 10. 84 75. 88 1. 5 8. 8 10. 84 27. 10 75. 88 1. 5 8. 8 61. 5 130.9 11, 382 10. 84 75.88 1. 5 8.8 10. 84 37. 94 75. 88 1. 5 8. 8 86. 1 130. 9 12,466 10.84 75.88 1. 5 8. 8 10.84 48. 78 75.88 1. 5 8. 8 110. 7 130.9 550 10. 84 75. 88 1. 5 8. 8 10. 84 75. 88 75. 88 1. 5 8. 8 135. 3 130. 9 14, 634 10. 84 75. 88 1. 5 8. 8 10. 84 75. 88 75. 88 1. 5 8. 8 172.0 130.9 16, 626

'Oxyalkylation-suseeptible.

TABLE VIII Time Solubility hrs.

Xylene Kerosene XXX I Soluble.

Insoluble. Dispersible. Do.

Do. Insoluble.

D0. Dlspersible o. Insoluble.

Do. Disperslble. Soluble.

D0. D0. D0. D0. Insoluble.

Do. Disperslble. Do. Soluble.

Do. Disperslble. D0. Soluble.

Do. Do.

TABLE VIII Max. Max Solubility Ex. temp., pres, Time, No. C. p. 5.1 hrs.

Water Xylene Kerosene -20 2 Emulsifiable. Insoluble 15-20 2% do Do. 15-20 3 do Do. 15-20 4 Insoluble Do. 15-20 2% .(1 D0. 15-20 2% .do. Do. 15-20 3 do. Do. 15-20 3% do. Do. -25 Soluble D0. 20-25 1 .do. Do. 20-25 1% Emuls Do. 20-25 2% 0... Do. 20-25 3 d0 D0. 20-25 4 Emulslfiable D0.

to insoluble. 20-20 .do D0. 20-25 D0. 20-25 Soluble. 20-25 Do. 20-25 D0. 20-25 Do. 20-25 D0. 20-25 Do. 20-25 Do. 2025 D0. 20-30 D0. 20-30 Do. 20-30 Dispersible. 20-30 Insoluble. 20-30 Do. 20-30 do Do. 20-30 Emulsifiable Do.

to soluble. 20-80 5 Soluble Do.

it n P ART 8 and 1s ecessary that the solvent be readily removed as,

The resin condensates which are employed as intermediate reactants are strongly basic. Initial oxyalkylation of these products with a monoepoxide or diepoxide either one can be accomplished generally, at least in the initial stage, without the addition of the usual alkaline catalyst such as those described in connection with oxyalkylation employing monoepoxides in Part 7 immediately preceding. As a matter of fact, the procedure is substantially the same as using a non-volatile monoepoxide such as glycide or methylglycide. However, during progressive oxyalkylation with a monoepoxide it is usually necessary to use a catalyst as previously described and, thus, there may or may not be sulficient catalyst present for the reaction with the diepoxide. Reference to the catalyst present includes the residual catalyst remaining from the oxyalkylation step in which the monoepoxide was used.

Briefly stated then, employing polyepoxides in combination with a nonbasic reactant the usual catalysts include alkaline materials, such as caustic soda, caustic potash, sodium methylate, etc. Other catalysts may be acidic in nature and are of the kind illustrated by iron and tin chloride. Furthermore, insoluble catalyst such as clay or specially prepared mineral catalysts have been used. if for any reason the reaction does not proceed rapidly enough with the diglycidyl ether or other analogous reactant then a small amount of finely divided caustic soda or sodium methylate can be employed as a catalyst. The amount generally employed would be 1% or 2%.

It goes without saying thatthe reaction can take place in an inert solvent, i. e., one that is not oxyalkylationsusceptible. Generally speaking, this is most conveniently an aromatic solvent such as xylene or a higher boiling coal tar solvent, or else a similar high boiling aromatic solvent obtained from petroleum. One can employ an oxygenated solvent such as the diethylether of ethyleneglycol, or the diethylether of propyleneglycol, or similar ethers, either alone or in combination with a hydrocarbon solvent. The selection of the solvent depends in part on the subsequent use of the derivatives or reaction products. If the reaction products are to be rendered solvent-free for example, by the use of vacuum distillation, then xylene or an aromatic petroleum solvent will serve. If the prodnot is going to be subjected to oxyalkylation subsequently, then the solvent should be one which is not oxyalkylationsusceptible. It is easy enough to select a suitable solvent if required in any instance but, everything else being equal, the solvent chosen should be the most economical one.

Example la The product was obtained by reaction between the diepoxide previously described as diepoxide 3A and oxyalkylated resin condensate 2c. Oxyalkylated condensate 20 has been described in previous Part Seven and was obtained by the oxyethylation of condensate 1b. The preparation of condensate 1b was described in Part 6, preceding. Details have been included in regard to both steps. Condensate 1b, in turn, was obtained from diethylamine and resin 2a; resin 2a, in turn, was obtained from para-tertiarybutylphenol and formaldehyde.

In any event, 317 grams of the oxyalkylated resin condensate previously identified as 2c were dissolved in approximately an equal weight of xylene. About 3 grams of sodium methylate Were added as a catalyst so the total amount of catalyst present, including residual catalyst from the prior oxyalkylation, was about 3.3 grams. 17 grams of diepoxide 3A were mixed with an equal weight of xylene. The initial addition of the diepoxide solution was made after raising the temperature of the reaction mass to about C. The diepoxide was added slowly over a period of one hour. During this time the temperature was allowed to rise to about 126 C. The mixture was allowed to reflux at about 132 C. using a phase-separating trap. A small amout of xylene was removed by means of a phase-separating trap so the refluxing temperature rose gradually to about C. The mixture was refluxed at this temperature for about 5 hours. At the end of this period the xylene which had been removed by means of the phase-separating trap was returned to the mixture. A small amount of material was Withdrawn and the xylene evaporated on a hot plate in order to examine the physical properties. The material was an amber, or light reddish amber, viscous liquid. It was insoluble in water; it was insoluble in gluconic acid, but it was soluble in xylene and particularly in a mixture of xylene and 20% methanol. However, if the material was dissolved in an oxygenated solvent and then shaken with 5% gluconic acid it showed a definite tendency to disperse, suspend, or form a sol, and particularly in a xylene-methanol mixed solvent as previously described, with or without the further addition of a little acetone.

Generally speaking, the solubility of these derivatives iS in line with expectations by merely examining the solubility of the preceding intermediates, to wit, the oxyalkylated resin condensates prior to treatment with the 'diepoxide. These materials, of course, vary from extremely water-soluble products due to substantial oxyethylation, to those which conversely are water-insoluble out xylenesoluble or even kerosene-soluble due to high stage oxypropylation. Reactions with diepoxicies or polyepoxides of the kind herein described reduce the hydrophile properties and increase the hydrophoce properties, i. e., generally make the products more soluble in kerosene or a mixture of kerosene and xylene, or in xylene, but less soluble in water. Since this is a general rule which applies throughout, for sake of brevity future reference to solubility will be omitted. i

The procedure employed, of course, is simple in light of what has been said previously and in eifect is a procedure similar to that employed in the use of glycide or methylglycide as oxyalkylating agents. See, for example, Part 1 of U. 8. Patent No. 2,602,062, dated July 1, 1952, to De Groote.

Various examples obtained in substantially the same manner are enumerated in the following tables:

TABLE XI 1 Prob. 11101.

Ex. No. v Oxyalkyl. 7 weight of Amount of Amount of resin conreaction product, grs. solvent densate product 6, 680 3, 340 l, 670 10, 900 2,180 1, 090 5, 330 2, 680 l, 340 1, 290 2, 580 1, 290 15, 750 3,150 1, 575 6, 680 3, 340 1, 670 10, 390 2, 078 1, 039 13, 350 2, 670 l, 335 5, 480 2, 740 1, 370 14,070 2, 814 1, 407 7, 730 3, 865 1, 933 11,000 2, 200 1, 13, 010 2, 502 1, 301 17, 280 3, 456 1, 728 18, 520 3, 704 1, 852

TABLE XII 'Prob. mol. Ex. No. Oxyalkyl. weight of Amount of Amount of resin conreaction product, grs. solvent densate product TABLE IX Ex. Oxy. Amt, Diep- Amt, Catalyst Xy- Molar Time of Max. No. resin congrs. oxide grs. (NaOCHa), lone, ratio reaction, temp., Color and physical state densate used grs. grs. hrs. G.

317 3A 17 3. 3 334 2:1 "5 Reddish amber resinous mass. 254 3A 8. 5 2. 7 273 2:1 5 Do. 251 3A 17 2. 7 268 221 5 162 D0. 314 3A. 8. 5 3. 2 323 2: 1 '5 Do. 385 3A 8. 5 3. 9 394 2: 1 '5. 5 170 Do. 317 3A 17 3. 3 334 2:1 5 168 Do. 251 3A 8. 5 2.6 260 2:1 5 165 Do. 325 3A 8. 5 3. 3 334 2:1 5 165 Do. 257 3A 17 2. 7 274 2: 1 5 164 D0. 343 3A 8. 5 3. 5 352 2:1 "5 170 D0. 370 3A 17 3.8 387 2:1 '6 167 D0. 269 3A 8.5 2. 8 278 2:1 5 165 Do. 317 3A 8.5 3.3 326 2:1 5. 5 165 D0. 212 3A 4.3 2. 2 216 2:1 15 160: D0. 227 3A 4. 3 2. 3 231 2:1 5 160 D0.

TABLE X Ex. Oxy. Amt, Dicp- Amt, Catalyst Xy- Molar Time of Max. No. resin congrs. oxide grs. (NaOCHa), lene, ratio reaction, temp, Color and physical state densate used grs. grs. 1 hrs. O.

317 B1 27.5 3. 5 345 2:1 4 155 Reddish amber resinous mass. 264 B1 13.8 2. 8 278 2:1 4 154 D0. 251 B1 27. 5 2. 8 279 2:1 4. 5 150 Do. 314 B1 13. 8 3. 3 328 2:1 -4. 5 152 D0. 385 B1 13.8 4. 0 399 2: l 4.5 150 D0. 317 B1 27.5 3. 5 345 2:1 5 150 D0. 251 B1 13.8 2. 7 255 2:1 4 155 Do. 325 B1 13. 8 3. 4 339 2: 1 4 157 D0. 257 B1 27.5 2. 9 285 2:1 4 154 Do. 343 B1 13. 8 3. 6 357 2:1 4. 5 150 Do. 370 B1 27. 5 4.0 398 2:1 4. 5 148 Do. 269 B1 13.8 2.8 283 2:1 4.5 150 D0. 317 B1 13. 8 3.3 331 2:1 4 152 D0. 212 B1 6. 9 2. 2 219 2:1 4 150 D0. 227 B1 6. 9 2. 3 234 2: 1 4 150 Do.

At times We have found atendency for an insoluble mass to form or at least to obtain incipient cross-linking or gelling even when the molal ratio is in the order of 2 moles of resin to one of diepoxide. We have found this can be avoided by any one of the following procedures or their equivalent. Dilute the resin or the diepoxide, or both, with an inert solvent, such as xylene or the like. In some instances an oxygenated solvent, such as the diethylether of ethyleneglycol may be employed. Another procedure which is helpful is to reduce the amount of catalyst used, or reduce the temperature of reaction by adding a small amount of initially lower boiling solvent, such as benzene, or use benzene entirely. Also, we have found it desirable at times to use slightly less than appar ently the theoretical amount of diepoxide, for instance, 90% to 95% instead of 100%. The reason for this fact may reside in the possibility that the molecular weight dimensions on either the resin molecule or the diepoxide molecule actually may vary from the true molecular weight by several percent.

The condensate can be depicted in a simplified form which, for convenience, may be shown thus:

(Amine) CH2(Resin)CH2(Amine) If such product is subjected to oxyalkylation reaction involves the phenolic hydroxyls of the resin structure and, thus, can be depicted in the following manner:

(Amine) CHz( Oxyalkylated Resin CH2 (Amine) Following such simplication the reaction with a polyepoxide, and particularly a diepoxide, would be depicted thus:

(Amine) Ofifloxyalkylaited Resin) CH (Amine) D.G.E.

l (Amine) OH2(Oxyalkylated Resin) CH2 (Amine) in which D. G. E. represents a diglycidyl ether as specified.

As has been pointed out previously, the condensation reaction may produce other products, including, for example, a product which may be indicated thus in light of what has been said previously:

[(Amine)CHz(Resin)] This product, since it is susceptible to oxyalkylation by means of the oxyalkylated phenolic hydroxyl groups and depending on the selection of the amine, may be susceptible to oxyalkylation in event a hydroxylated amine or polyamine had been used, and may be indicated in the following manner:

[Oxyalkylated(Arnine) CHz(Resin)] When a diglycidyl ether is employed one would obviously obtain compounds in which two molecules of the kind described immediately preceding are united in a manner comparable to that previously described, which may be indicated thus:

Oxyalkylated (Amine) CL; (Resin) I D.G.E.

Oxyalkylated (Amine) CH (Resin) Likewise, it is obvious that the two different types of oxyalkylation-susceptible compounds may combine so as to give molecules which may be indicated thus:

I (Amine)CHz(Oxyalkylated Resin)CHz(Amine) I l D.G.E.

Oxyalkylated (Amine) CH2 (Resin) Oxyalkylated (Amine) CH (Amine) D.G.E.

| I (Amine)CH (Oxya1kylated Resin)CH2 (Amine) i I Oxyalkylated(Amine)OHi(Amine) 1 D.G.E.

l i Oxyalkylated (Amine) CHAResin) I Oxyalkylated (Amine) 0H (Amine) D.G.E.

I I Oxyalkylated (Amine) CH2 (Amine) l Actually, the product obtained by reaction with a diglycidyl ether could show considerably greater complexity due to the fact that, as previously pointed out, the condensate reaction probably does not yield a hundred percent condensate in absence of other byproducts. All this simply emphasizes one fact, to wit, that there is no suitable method of characterizing the final reaction product except in terms of method of manufacture.

PART 9 Conventional demulsifying agents employed in the treatment of oil field emulsions are used as such, or after dilution with any suitable solvent, such as water, petroleum hydrocarbons, such as benzene, toluene, xylene, tar acid oil, cresol, anthracene oil, etc. Alcohols, particularly aliphatic alcohols, such as methyl alcohol, ethyl alcohol, denatured alcohol, propyl alcohol, butyl alcohol, hexyl alcohol, octyl alcohol, etc., may be employed as diluents. Miscellaneous solvents such as pine oil, carbon tetrachloride, sulfur dioxide extract obtained in the refining of petroleum, etc., may be employed as diluents. Similarly, the material or materials employed as the demulsifying agent of our process may be admixed with one or more of the solvents customarily used in connection with conventional demulsifying agents. Moreover, said material or materials may be used alone or in admixture with other suitable well-known classes of demulsifying agents.

It is well known that conventional demulsifying agents may be used in a water-soluble form, or in an oil-soluble form, or in a form exhibiting both oiland water-solubility. Sometimes they may be used in a form which exhibits relatively limited oil-solubility. However, since such reagents are frequently used in a ratio of 1 to 10,000 or 1 to 20,000, or 1 to 30,000, or even 1 to 40,000, or 1 to 50,000 as in desalting practice, such an apparent insolubility in oil and water is not significant because said reagents undoubtedly have solubility within such concentrations. This same fact is true in regard to the material or materials employed as the demulsifying agent of our process.

In practicing the present process, the treating or demulsifying agent is used in the conventional way, well known to the art, described, for example, in Patent 2,626,929, dated January 27, 1953, Part 3, and reference is made thereto for a description of conventional procedures of demulsifying, including batch, continuous, and

. 3 9 doWn-the-hole demulsification, the process essentially involving introducing a small amount of demulsifier into a large amount of emulsion with adequate admixture with or without the application of heat, and allowing the mixture to stratify.

'In many instances the oxyalkylated products herein specified as demulsifiers can be conveniently used without dilution. However, as previously noted, they may be diluted as desired with any suitable solvent. For instance, by mixing 75 parts by weight of an oxyalkylated derivative, for example, the product of Example 3e with 15 parts by weight of xylene-and 10 parts by weight of isopropyl alcohol, an excellent demulsifier is obtained. Selection of the solvent will vary, depending upon the solubility characteristics of the oxyalkyla'ted product, and of course will be dictated in part by economic considerations, i. e., cost.

As noted above, the products herein described may be used not only in diluted form,.but also may be used admixed with some other chemical demulsifier. A mixture with illustrates such combination is the following:

Oxyalkylated derivative, for. example, the product of Example 3e, 20%;

A cyclohexylamine salt of a polypropylated naphthalene monosulfonic acid, 24%;

An ammonium salt of a polypropylated naphthalene monosulfonic acid, 24%; v

A sodium salt of oil-soluble mahogany petroleum sulfonic acid, 12%; p

A high-boiling aromatic petroleum solvent, 15%;

Isopropyl alcohol, 5%.

The above proportions are all weight percents.

Having thus described our invention what we claim stage phenol-aldehyde resin having an average molecular weight corresponding to at least 3 and not over 6' phenolic nuclei per resin molecule; said resin being difunctionalonly in regard to methylol-fonning reactivity; said resin being derived-by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and sub' stituted in the 2,4,6 position; (b) a basic nonhydroxylated' secondary monoamine having not more than 32 carbon atoms inany group attached to the amino nitrogen atom, and (c) formaldehyde; said condensation reaction being conducted at' a temperature sufiiciently high to eliminate Water and below the pyrolytic point of the reactants and resultants of reaction; and with the proviso that the resinous condensation product resulting from the process be heat stable and oxyalkylation-susceptible; followed 'as a second step by (B) oxyalkylation by means of an alphabetaalkylene oxide having not more than 4 carbon atoms andselected from the-class; consisting of ethylene oxide,

propylene oxide, butylene" oxide, glycide and methyl glycide; andthen completing the reactionby a third step of-(C); reacting saidoxyalkylated resin condensate with a phenOl c polyepoxide free from reactive functional groups other than epoxy. and hydroxyl groups and cogenerically associated'cofnpoundsformed in the preparation of said polyepoxides; said epoxides being monotriers and low molal polymers not exceeding the tetramer s; said polyepoxides being selected'fr'om the class consisting of (eta) compounds where the phenolic nuclei are directly joined withoutan. intervening bridge radical, and (bb). compounds containing a radical in which 2 phenolic nuclei are joined by a divalent'radical selected from the class consisting of ketone residues formed by the, elimination of the ket'onic oxygen atom, and aldehyde residues obtained by the elimination of the aldheyde oxygen atom, the divalent radical the'divalent radical, the divalent sulfone radical and divalent monosulfide radical S, the divalent radical CH2SCH2, and the divalent disulfide radical SS said phenolic portion of the polyepoxide being obtained from a phenol of the structure .in which R, R", and R represent a member of the sultants of reaction; and with the final proviso that the ratio of reactants be 2 moles of theoxyalkylatedresin condensate to 1 mole of the phenolic polyepoxide.

. 2. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier; said demulsifier being obtained by a three-step manufacturing process involving 1) condensation; (2) oxyalkylation with a monoepoxide; and (3) oxyalkylation with a polyepoxide; said functional phenols; saidphenol being of the formula in Which R is an aliphatic hydrocarbon radical having at least v4 and not morefthan; 24 carbon atoms and'substituted in the 2,4,,6 position; (b) a basic nonhydroxylated secondary monoamine having"n0t more than 32 carbon atoms in any group, attached to the amino mtro- 7 gen atom, and (0) formaldehyde; said condensauon reac- 

1. A PROCESS FOR BREAKING PETROLEUM EMULSIONS OF THE WATER-IN-OIL TYPE CHARACTERIZED BY SUBJECTING THE EMULSION TO THE ACTION OF A DEMULSIFIER; SAID DEMULSIFER BEING OBTAINED BY A THREE-STEP MANUFACTURING PROCESS INVOLVING (1) CONDENSATION; (2) OXYALKYLATION WITH A MONOEPOXIDE; AND (3) OXYALKYLATION WITH A POLYEPOXIDE; SAID FIRST MANUFACTURING STEP BEING A METHOD OF (A) CONDENSING (A) AN OXYALKYLATION-SUSCEPTIBLE, FUSIBLE, NONOXYGENATED ORGANIC SOLVENT-SOLUBLE, WATER-INSOLUBLE, LOWSTAGE PHENOL-ALDEHYDE RESIN HAVING AN AVERAGE MOLECULAR WEIGHT CORRESPONDING TO AT LEAST 3 AND NOT OVER 6 PHENOLIC NUCLEI PER RESIN MOLECULE; SAID RESIN BEING DIFUNCTIONAL ONLY IN REGARD TO METHYLOL-FORMING REACTIVITY; SAID RESIN BEING DERIVED BY REACTION BETWEEN A DIFUNCTIONAL MONOHYDRIC PHENOL AND AN ALDEHYDE HAVING NOT OVER 8 CARBON ATOMS AND REACTIVE TOWARD SAID PHENOL; SAID RESIN BEING FORMED IN THE SUBSTANTIAL ABSENCE OF TRIFUNCTIONAL PHENOLS; SAID PHENOL BEING OF THE FORMULA 